Article
Chemistry, Multidisciplinary
Henrik Gulyas, Shigetaka Hayano, Adam Madarasz, Imre Papai, Mark Szabo, Agota Bucsai, Eddy Martin, Jordi Benet-Buchholz
Summary: By tuning the electron donor capacity of ligands, air-stable solid adducts of tungsten and molybdenum alkylidenes can be prepared, which can spontaneously release active catalysts in solution.
COMMUNICATIONS CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Kenta Mori, Midori Akiyama, Ko Inada, Yutaka Imamura, Yuichiro Ishibashi, Yusuke Takahira, Kyoko Nozaki, Takashi Okazoe
Summary: By introducing a seven-membered N-heterocyclic carbene (NHC) ligand, a significant increase in catalyst turnover number (TON) was achieved in the cross-metathesis of tetrafluoro-ethylene (TFE) and vinyl ethers. This study provides a new approach to enhance catalytic efficiency in such reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Or Eivgi, Anna Vaisman, N. Gabriel Lemcoff
Summary: The ligand shell that surrounds an active metal center plays a crucial role in determining the reactivity and properties. This study presents new ruthenium indenylidene complexes with a combination of phosphite olefin metathesis precatalysts and cyclic alkyl amino carbene (CAAC) ligands, which show efficient photoactivity and robust stability. These catalysts exhibit formidable latency at ambient temperatures, allowing for a wide range of olefin metathesis reactions and efficient recycling for multiple reaction cycles under air.
Article
Multidisciplinary Sciences
Yanqing Ge, Shaofeng Huang, Yiming Hu, Lei Zhang, Ling He, Sebastian Krajewski, Michael Ortiz, Yinghua Jin, Wei Zhang
Summary: Alkyne metathesis catalysts typically face limitations due to high moisture/air sensitivity, restricting their broad applicability. The authors present efficient alkyne metathesis catalysts that can operate under open-air conditions with a broad functional group tolerance.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Shaofeng Li, Shijie Feng, Yali Zhou, Chao Liu, Bo Chen, Xiangyou Xing
Summary: Asymmetric olefin metathesis is a powerful strategy for stereocontrolled synthesis, and this study introduces a new series of cyclometalated stereogenic-at-Ru catalysts that enable highly efficient asymmetric ring opening/cross-metathesis (AROCM) and asymmetric ring-closing metathesis (ARCM) reactions. These catalysts can be easily accessed with either right-handed or left-handed configurations at the Ru center. The right-handed chiral Ru catalysts enable the synthesis of densely functionalized cyclopentanes with excellent stereo- and enantioselectivities, while the left-handed chiral Ru catalysts facilitate the production of cyclic ethers and amides with tertiary or quaternary carbon stereocenters with high enantioselectivities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Seongwook Park, Seunghwan Byun, Huijeoung Ryu, Hyungwoo Hahm, Junseong Lee, Sukwon Hong
Summary: Novel ruthenium catalysts bearing azobenzene groups were developed for olefin metathesis reactions, demonstrating an on-off switching ability in ring-closing metathesis reactions depending on UV irradiation. Various types of olefin metathesis reactions, such as ring-opening metathesis, cross-metathesis, and ethenolysis, exhibited photoswitching phenomena. The reversible feature of photoswitching was confirmed by observing the photoisomerization of azobenzene-bearing cyclic(alkyl)(amino)carbene ligands and the corresponding ruthenium catalysts using UV-vis spectroscopy.
Article
Chemistry, Inorganic & Nuclear
Seunghwan Byun, Da-Ae Park, Seyong Kim, Sunghyun Kim, Ji Yeon Ryu, Junseong Lee, Sukwon Hong
Summary: A series of acyclic aminooxycarbene (AAOC)-ligated ruthenium metathesis catalysts were developed and exhibited outstanding catalytic efficiencies and selectivities in the ethenolysis of methyl oleate and cis-cyclooctene. The ambiphilic character of AAOC ligands, combining strong sigma-donors and pi-acceptors, contributed to the enhancement of catalytic activity and selectivity of the ruthenium catalysts. This research represents a rare example of acyclic carbene-ruthenium catalysts demonstrating high catalytic efficiency and excellent selectivity in olefin metathesis reactions.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Natalia Barteczko, Miroslawa Grymel, Anna Chrobok
Summary: Over the past 30 years, many strategies have been developed to immobilize well-defined metathesis catalysts on solid supports. The use of heterogeneous catalysis resulted in increased purity of the product and the possibility of recycling the catalyst. This review focuses on the short history of heterogeneous catalysts used in olefin metathesis, with particular emphasis on examples from recent years. It mainly discusses the immobilized ruthenium alkylidene complexes based on ionic liquids as a new promising approach, including the noncovalent immobilization that has gained recent interest. The methods of attaching catalysts and types of carriers are also presented. Homogeneous catalysts are discussed to highlight the influence and potential of immobilization on the activity and selectivity of heterogeneous catalysts in olefin metathesis.
CATALYSIS COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Christian O. Blanco, Deryn E. Fogg
Summary: Water has a significant impact on olefin metathesis, as it can react with catalysts and cause decomposition of the reaction intermediates. This poses a challenge for demanding reactions in water-rich environments, as metathesis is typically noncatalytic under these conditions.
Article
Chemistry, Multidisciplinary
Yuichi Okazaki, Seiji Oda, Akihiko Takamatsu, Shogo Kawaguchi, Hirofumi Tsukasaki, Shigeo Mori, Shunsuke Yagi, Hidekazu Ikeno, Ikuya Yamada
Summary: The rational design of highly active catalysts for the oxygen evolution reaction (OER) is important for energy-conversion applications. Postspinel-structured oxides, CaB2O4, exhibit higher OER activities due to their lower charge-transfer resistances. A density-functional-theory calculation suggests a novel mechanism of lattice oxygen pairing with adsorbed oxygen, which results in the lowest theoretical OER overpotential.
Article
Multidisciplinary Sciences
Thotsatham Takkawatakarn, Supareak Praserthdam, Sippakorn Wannakao, Joongjai Panpranot, Piyasan Praserthdam
Summary: The study found that the addition of MgO affected the generation of new species of coke deposited on WO3/SiO2 and MgO itself, and the difference in reaction temperature (300 vs. 450 degrees C) led to different types and temperatures of coke formation, indicating a significant impact of temperature changes on reaction pathways and outcomes.
SCIENTIFIC REPORTS
(2021)
Article
Chemistry, Physical
Peng Ma, Jiaren Zhang, Xiaqian Wu, Jianhui Wang
Summary: Phosphine-free ruthenium benzylidene complexes with imidazole ligands have been reported. These catalysts are effective for high-temperature ring-closing metathesis (RCM) and cross-metathesis (CM) reactions, unlike the commonly used phosphine-containing N-heterocyclic carbene-based ruthenium catalysts which exhibit side reactions. This discovery paves the way for the development of more selective ruthenium metathesis catalysts for reactions requiring harsh conditions.
Article
Chemistry, Multidisciplinary
Noy B. Nechmad, Victoria Kobernik, Naziha Tarannam, Ravindra Phatake, Or Eivgi, Sebastian Kozuch, N. Gabriel Lemcoff
Summary: A novel catalyst Ru-S-CF3-I was synthesized with distinct activity and selectivity profiles for olefin metathesis reactions. The combination of photoisomerization and photochemical release of chloride ions allows for a wide scope of photoinduced olefin metathesis reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Ravindra S. Phatake, Noy B. Nechmad, Ofer Reany, N. Gabriel Lemcoff
Summary: A selective ring-closing metathesis (RCM) reaction using latent sulfur chelated ruthenium iodide benzylidenes as catalysts, activated by thermal and photochemical stimuli, has been reported. This method enables the formation of large macrocycles with high yields, especially for dienes with one terminal alkene and one internal double bond. For substrates containing two internal double bonds, a sacrificial methylene donor can be used to obtain the desired products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Adrian Sytniczuk, Pawel Malecki, Anna Kajetanowicz, Karol Grela
Summary: The activity of new indenylidene complexes with two unsymmetrical N-heterocyclic carbene (NHC) ligands was investigated. They were found to be effective in both straightforward olefin metathesis reactions and more demanding processes.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Saigopalakrishna S. Yerneni, Sushil Lathwal, Julia Cuthbert, Kriti Kapil, Grzegorz Szczepaniak, Jaepil Jeong, Subha R. Das, Phil G. Campbell, Krzysztof Matyjaszewski
Summary: This paper reports a localized delivery platform for therapeutic exosomes using tethered poly-(ethylene oxide) hydrogels. By tuning the crosslinking density of the polymer network and using photodegradable tethers, controlled release of exosomes was achieved, resulting in improved efficacy and extended release duration.
Article
Polymer Science
Sajjad Dadashi-Silab, Khidong Kim, Francesca Lorandi, Grzegorz Szczepaniak, Stephanie Kramer, Linda Peteanu, Krzysztof Matyjaszewski
Summary: In this study, a dual photoredox catalytic system was developed for photoinduced ATRP under red-light irradiation, avoiding the problems associated with UV light activation of the catalyst. The system showed oxygen tolerance due to the consumption of oxygen in the photoredox reactions, resulting in well-controlled polymerizations without the need for deoxygenation processes.
Article
Polymer Science
Michael R. Martinez, Sylwia Dworakowska, Adam Gorczynski, Grzegorz Szczepaniak, Ferdinando De Luca Bossa, Krzysztof Matyjaszewski
Summary: The effect of monomer structure on polymerization reactions was studied in aqueous media. It was found that longer macromonomers polymerized faster, while the OEO side chain at the alpha position of isomeric acrylates significantly slowed down the reaction.
JOURNAL OF POLYMER SCIENCE
(2022)
Article
Polymer Science
Mateusz Olszewski, Jaepil Jeong, Grzegorz Szczepaniak, Sipei Li, Alan Enciso, Hironobu Murata, Saadyah Averick, Kriti Kapil, Subha R. Das, Krzysztof Matyjaszewski
Summary: In this study, a new sulfoxide-containing monomer, MSEAM, was synthesized and well-defined polymers were prepared using PICAR ATRP. The results showed that PMSEAM exhibited excellent biocompatibility and relatively low toxicity.
Article
Polymer Science
Rongguan Yin, Yuqi Zhao, Adam Gorczynski, Grzegorz Szczepaniak, Mingkang Sun, Liye Fu, Khidong Kim, Hanshu Wu, Michael R. Bockstaller, Krzysztof Matyjaszewski
Summary: An alternating P-(MMA/BA) copolymer was synthesized using the ARGET ATRP method, and subsequent postpolymerization modifications were performed. The modified copolymer showed different architecture compared to gradient and statistical copolymers, with a narrower range of glass transition.
Article
Chemistry, Multidisciplinary
Kriti Kapil, Grzegorz Szczepaniak, Michael R. R. Martinez, Hironobu Murata, Arman Moini Jazani, Jaepil Jeong, Subha R. R. Das, Krzysztof Matyjaszewski
Summary: In this study, hyperbranched polymethacrylates were synthesized by green-light-induced atom transfer radical polymerization (ATRP) under biologically relevant conditions. By using a water-soluble SBA inibramer as a inducer during the copolymerization of methacrylate monomers, well-defined branched polymethacrylates can be obtained in less than 30 minutes with predetermined molecular weights, tunable degree of branching, and low dispersity values (1.14 <= D <= 1.33). Moreover, SBA inibramer enables the synthesis of bioconjugates with a well-controlled branched architecture.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Polymer Science
Mingkang Sun, Grzegorz Szczepaniak, Sajjad Dadashi-Silab, Ting-Chih Lin, Tomasz Kowalewski, Krzysztof Matyjaszewski
Summary: Cu-catalyzed atom transfer radical polymerization is a powerful method for preparing well-defined (co)polymers. This minireview summarizes the development of cocatalysts for regenerating Cu-I complex activators during polymerizations. Recent developments of photochemical cocatalysts and methods to study their properties and roles are also discussed.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Julian Sobieski, Illia Ruzhylo, Grzegorz Szczepaniak, Adam Gorczynski, Krzysztof Matyjaszewski, Eric Manoury, Rinaldo Poli
Summary: Simple synthetic routes for the regioselective deuteration of tris[2-(dimethylamino)ethyl]amine (Me6TREN) variants are described. Formation of imine with formaldehyde-d(2) from tris(2-aminoethyl)amine (TREN) and subsequent reduction with NaBD4 resulted in N[CH2CH2N(CD3)(2)](3) or d(18)-Me6TREN in 79% yield. A trisubstitution protocol from 2-bromo-N,N-dimethylacetamide and ammonium carbonate, followed by reduction of the N(CH2CONMe2)(3) intermediate with lithium aluminum deuteride, afforded N[CH2CD2N(CH3)(2)](3) or (d(6)-arm)-Me6TREN in three steps and 52% overall yield. A similar protocol using 2-bromo-N,N-dimethyl-d(2)-acetamide, obtained from d(4)-acetic acid in two steps, and reduction of the N(CD2CONMe2)(3) intermediate with lithium aluminum hydride, resulted in N[CD2CH2N(CH3)(2)](3) or (d(6)-cap)-Me6TREN in four steps and 13% overall yield.
Article
Polymer Science
Dirk J. Schild, Juliana Bem, Grzegorz Szczepaniak, Arman Moini Jazani, Krzysztof Matyjaszewski
Summary: We report a photoinduced initiators for continuous activator regeneration atom transfer radical polymerization (PICAR ATRP) using sodium pyruvate and blue light (λ(max) = 456 nm). Water-soluble oligo(ethylene oxide) methyl ether methacrylate (OEOMA(500)) was polymerized under biologically relevant conditions. Well-defined polymers with high molecular weights and low dispersity were synthesized in less than 60 min using Cu/Fe dual catalysis and without deoxygenation.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Polymer Science
Kriti Kapil, Arman Moini Jazani, Grzegorz Szczepaniak, Hironobu Murata, Mateusz Olszewski, Krzysztof Matyjaszewski
Summary: Photoinduced ATRP techniques using green light and dual catalysis have been developed for efficient and controlled polymerization. This method allows rapid synthesis of well-defined polymers without the need for deoxygenation, overcoming the limitations of UV light-induced polymerization. The system also enables temporal control and synthesis of various hydrophilic acrylate monomers.
Article
Chemistry, Multidisciplinary
Jaepil Jeong, So Young An, Xiaolei Hu, Yuqi Zhao, Rongguan Yin, Grzegorz Szczepaniak, Hironobu Murata, Subha R. Das, Krzysztof Matyjaszewski
Summary: This study presents an approach to convert biomass RNA into an acrylic crosslinker by acyl imidazole chemistry, allowing for the fabrication of materials with tunable properties. It also explores reversible-deactivation radical polymerization methods and metallization of the biomass RNA-based material, expanding the opportunities in biomass-based biomaterial fabrication.
Article
Chemistry, Multidisciplinary
Francesca Lorandi, Marco Fantin, Hossein Jafari, Adam Gorczynski, Grzegorz Szczepaniak, Sajjad Dadashi-Silab, Abdirisak A. Isse, Krzysztof Matyjaszewski
Summary: Linear free energy relationships (LFERs) were used to establish the reductive cleavage of the C(sp(3))-X bond in alkyl halides (RX) by Cu complexes. The activation rate constant, k(act), for 107 Cu complex/RX couples in 5 different solvents were effectively interpolated by an equation. The set of descriptors determined the fundamental properties of Cu complexes and RX, which need to be considered when designing atom transfer radical reactions. A multivariate linear regression (MLR) approach was adopted to develop an objective model that surpassed the predictive capability of the LFER equation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xiaolei Hu, Grzegorz Szczepaniak, Anna Lewandowska-Andralojc, Jaepil Jeong, Bingda Li, Hironobu Murata, Rongguan Yin, Arman Moini Jazani, Subha R. Das, Krzysztof Matyjaszewski
Summary: This article introduces the first example of fully oxygen-tolerant red/NIR-light-mediated photoinduced atom transfer radical polymerization under biologically relevant conditions, using commercially available methylene blue as the catalyst. The method exhibits excellent oxygen tolerance and enables high-throughput synthesis of well-defined polymers and DNA-polymer bioconjugates in a short time.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jaepil Jeong, Xiaolei Hu, Hironobu Murata, Grzegorz Szczepaniak, Marta Rachwalak, Anna Kietrys, Subha R. R. Das, Krzysztof Matyjaszewski
Summary: Combining synthetic polymers with RNA allows for creating RNA-based materials with unique functions. By developing an acylation reagent, we achieved the direct incorporation of an atom transfer radical polymerization (ATRP) initiator into both synthetic oligoribonucleotides and natural biomass RNA. This approach enables the grafting of polymer chains from RNA and the synthesis of RNA-polymer hybrids with narrow molecular weight distributions, including RNA bottlebrushes, hydrogels, and stimuli-responsive materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Grzegorz Szczepaniak, Jaepil Jeong, Kriti Kapil, Sajjad Dadashi-Silab, Saigopalakrishna S. Yerneni, Paulina Ratajczyk, Sushil Lathwal, Dirk J. Schild, Subha R. Das, Krzysztof Matyjaszewski
Summary: This study developed a dual photoredox/copper catalysis method that allows photoinduced atom transfer radical polymerization under green light irradiation, with high oxygen tolerance and well-controlled synthesis of polymers.
Article
Chemistry, Physical
Zi-Ye Liu, Qian-Yu Wang, Ji-Ming Hu
Summary: In this study, a layered carbon dot composite catalyst (NiFe LDH@CDs) was prepared using a one-step coprecipitation method, without the need for heating or hydrothermal treatment. The CD-functionalized catalyst facilitated rapid charge transfer and accelerated the oxygen evolution reaction. Additionally, the heterojunction structure formed between NiFe LDH and CDs efficiently suppressed photoelectron-hole recombination.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Rohit Kumar, Ankit Kumar Srivastava, Palaniyappan Nagarasu, Vedichi Madhu, Ekambaram Balaraman
Summary: We designed and synthesized a NN-CoII bidentate complex and used it for the amination of alcohols under mild and solventless conditions. The complex exhibited good reactivity towards both primary and sterically hindered secondary alcohols, providing high yields of amines. The pyrazole moiety in the ligand played a crucial role in the reaction. Furthermore, we demonstrated the reusability of the complex as a homogeneous cobalt catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shivanand Chettri, Liang-Ting Wu, Sagarmani Rasaily, Debesh Sharma, Bikram Gurung, Rajani Dewan, Sudarsan Tamang, Jyh-Chiang Jiang, Anand Pariyar
Summary: Replicating the enzymatic surface microenvironment in vitro is challenging, but constructing an analogous model could facilitate our understanding of surface effects and aid in developing an efficient bioinspired catalytic system. In this study, five unique Cu2O morphologies were generated, and the surface morphology variations were found to be a consequence of differences in the exposure of low-index facets. The reactivity of Cu2O was found to be influenced by the proportion of {110} planes, with r-Cu2O exhibiting the highest reactivity.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Yong Tang, Jianhao Qiu, Dingliang Dai, Guanglu Xia, Lu Zhang, Jianfeng Yao
Summary: Defect engineering has been shown to improve the photocatalytic performance. This study investigated the use of defect-rich UiO-66-NH2 wrapped by ZnIn2S4 as a catalyst for photocatalytic H2O2 production. The defects in UiO-66-NH2 enhanced O-2 adsorption and charge separation, leading to higher H2O2 yield. The insights from this work can advance the research in defect engineering of MOFs and photocatalytic H2O2 synthesis.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Ruiyang Qu, Shuxin Mao, Jana Weiss, Vita A. Kondratenko, Evgenii V. Kondratenko, Stephan Bartling, Haifeng Qi, Annette-Enrica Surkus, Kathrin Junge, Matthias Beller
Summary: The hydrogenation of amides, a challenging reaction usually performed at high temperatures, has been achieved under milder conditions using a new Pt-MoOx/TiO2 catalyst. This catalyst system enables the selective hydrogenation of various amides and imides.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Xiaoran Niu, Ao Wang, Lei Tong, Lei Wang, Yuan Kong, Chenliang Su, Hai-Wei Liang
Summary: This study introduces a novel intermetallic PdCu3 catalyst supported on defective nanodiamond-graphene (ND@G), which exhibits high selectivity (95%) and remarkable activity (turnover frequency: 2940 h(-1)), six times higher than that of the commercial Lindlar catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Review
Chemistry, Physical
Zhiyuan Zheng, Yiming Yue, Hongying Zhuo, Qinggang Liu, Yanqiang Huang
Summary: This review presents the recent research advances on single-atom catalysis for deep reduction of CO2. Detailed introductions and summaries were classified into three categories based on proton-coupled multi-electron transfer approaches: strengthening metal-support interaction, rational design and regulation of coordination environment, and development of SACs with multi-atom active sites. The challenges and future research directions in the field of SACs for CO2 reduction are also proposed.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shiv Kumar, Paramita Datta, Anup Bhunia, Swadhin K. Mandal
Summary: This article reports a transition-metal-free process for in situ denitrogenation of tosylhydrazones, resulting in the production of various sulfones. The authors used a phenalenyl-based odd alternant hydrocarbon as a photoredox catalyst, which acted as a potent oxidant to facilitate the denitrogenation reaction. The method showed wide functional-group tolerance and high yields, making it suitable for late-stage modification of natural products.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
L. A. Luque-Alvarez, J. Gonzalez-Arias, F. Romero-Sarria, T. R. Reina, L. F. Bobadilla, J. A. Odriozola
Summary: Currently, the production of acetic acid through the carbonylation reaction of methanol has limitations, leading to the exploration of alternative methods using heterogeneous catalysts. This study investigates the methanol carbonylation reaction over a Cu-H-MOR catalyst and proposes a reaction mechanism based on the catalytic behavior and performance of the catalyst. The results provide insights into the reaction mechanism and the involvement of acid and redox centers.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
